CN107649161A - A kind of codope Rutile Type TiO2The preparation method of nanometer rods - Google Patents
A kind of codope Rutile Type TiO2The preparation method of nanometer rods Download PDFInfo
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- CN107649161A CN107649161A CN201710828724.9A CN201710828724A CN107649161A CN 107649161 A CN107649161 A CN 107649161A CN 201710828724 A CN201710828724 A CN 201710828724A CN 107649161 A CN107649161 A CN 107649161A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 21
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 20
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005554 pickling Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000013461 design Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910011208 Ti—N Inorganic materials 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000000187 Abnormal Reflex Diseases 0.000 description 1
- 240000008100 Brassica rapa Species 0.000 description 1
- 235000011292 Brassica rapa Nutrition 0.000 description 1
- 206010021089 Hyporeflexia Diseases 0.000 description 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
A kind of codope Rutile Type TiO2The preparation method of nanometer rods, belongs to TiO2The technical field of nanometer polymerization body, using titanium carbide as raw material, distribute it in water, then add ethylenediamine, scattered 20 30min, feed liquid after will be scattered is added in reactor, at 170 190 DEG C of temperature, reacts 5 6h, take out, 20 DEG C are cooled to, through centrifuging, washing, dry, obtains codope Rutile Type TiO2Nanometer rods.Preparation method of the present invention is simple, realizes one-step synthesis doping C, the Rutile Type TiO of N element2Nanometer rods.
Description
Technical field
The invention belongs to TiO2The technical field of nanometer polymerization body, it is related to Rutile Type TiO2The doping of nanometer rods, is specifically related to
A kind of and codope Rutile Type TiO2The preparation method of nanometer rods.Preparation method of the present invention realizes one-step synthesis doping C, N
The Rutile Type TiO of element2Nanometer rods.
Background technology
As the economic spring tide of reforming and opening up to the outside world swept over the country after 30 or 40 years, environment and energy problem seriously constrain it is current I
State's economy grows continuously and fast.Materialogy research in recent years shows：TiO2As a kind of wide band gap semiconducter, in photochemistry and
There are many advantages in photocell field, is the optimal preferred material for solving above-mentioned two hang-up.
Titanium dioxide (TiO2) semiconductor functional material, due to its low cost, non-toxic, high surface and high stability
The advantages that, be widely used in photocatalysis, solar cell, electrochromic effect device, moisture sensor device, antibacterial device and
The fields such as spintronics devices.But because its energy gap is 3.2eV, causes it to be only capable of directly absorption and be less than 388nm wavelength
Sunshine, it is impossible to visible ray is effectively absorbed, so as to limit TiO2Application in actual photocatalysis and opto-electronic conversion.
The content of the invention
The present invention is to solve the above problems, provide a kind of codope Rutile Type TiO2The preparation method of nanometer rods, has
Effect reduces TiO2TiO can have been widened with band gap2Light absorption range.
The present invention is to realize that the technical scheme that its purpose uses is：
A kind of codope Rutile Type TiO2The preparation method of nanometer rods, using titanium carbide as raw material, distribute it in water,
Then ethylenediamine is added, disperses 20-30min, the feed liquid after disperseing is added in reactor, at 160-180 DEG C of temperature, instead
5-6h is answered, takes out, is cooled to 20 DEG C, through centrifuging, washing, dry, obtains codope Rutile Type TiO2Nanometer rods.
The mass volume ratio of titanium carbide and ethylenediamine is (0.06g-0.30g)：(4mL-8mL).
It is distilled water to be distributed in water water used, and the mass volume ratio of titanium carbide and distilled water is (0.06g-
0.30g)：(16mL-20mL).
During washing, first with 2% watery hydrochloric acid pickling 2 times, then washed 3 times with absolute ethyl alcohol, finally with distillation washing 3 times.
When drying, it is dried using thermostatic drying chamber, drying temperature is 60-80 DEG C, drying time 10-12h.
Scattered to use ultrasonic disperse, it is 40-60Hz to control ultrasonic disperse frequency.
The reactor uses hydrothermal reaction kettle, and the volume of reactor is 6-13 times of ethylenediamine volume used.
The beneficial effects of the invention are as follows：
Preparation method one-step synthesis of the present invention adulterates C, the Rutile Type TiO of N element2Nanometer rods, C, N element doping
Effectively reduce TiO2It can more effectively realize that table (boundary) surface charge separates with band gap, the formation of nanorod structure, increase light
Raw charge life, so as to be converted by a series of optical-electronics-chemical energy, the toxic pollutant in decomposition water or air,
Or electric energy is converted into using solar energy, while also there is the effect for improving stream transport factor.
Existing C, N adulterate TiO2Although can be with a certain degree of absorption widened to visible ray, because light is rotten
Erosion and electric charge compound influence again, are unable to maintain that visible light catalysis activity, and this is the bottleneck faced at present, and the present invention
Solve the problems, such as.The incorporation of nitrogen can make TiO2Band-gap energy between lattice reduces, but can equally bring Lacking oxygen to increase, and makes
Increase into electronics and hole-recombination speed, so as to cause electron-hole recombination rate high, the present invention by the long-term analysis of some and
Research, finally found that reason is C, N codope to TiO2C, N codope TiO of effect, various concentrations, form etc.2Influence big
Differ, in further studying, these are all caused by preparation method.The present invention is raw material by using titanium carbide,
Reaction, which is carried out, with ethylenediamine realizes C, N codope, top of valence band and the band density increase nearby of conduction band bottom in the doping system of acquisition, from
And the transition probability of electronics is added, add absorption efficiency.The control of titanium carbide and ethylenediamine ratio so that N doping is formed
Inside band gap state sufficiently close to TiO2Conduction band and produce electronics coupled, it is compound so as to reduce electron-hole.Titanium carbide is first
Scattered, the control for then adding ethylenediamine redisperse and jitter time is in order that the codope Rutile Type TiO obtained2Nanometer
The particle diameter of rod is small and particle diameter distribution is uniform, nano-particle good dispersion, is acted on by dimensional quantum, improves photocatalytic activity.
The control of 160-180 DEG C of reaction temperature, reaction time 5-6h, the codope Rutile Type TiO of acquisition can be made2Nanometer rods are can
The hyporeflexia in Jian Guang areas, so that participating in the light quantity subnumber increase of light-catalyzed reaction, photoresponse scope is extended, so as to further
Improve the response to visible ray.
N of the present invention doping exists in the form of calking rather than displacement format, N existing for calking form formed Ti-N and
Ti-O collective effect, with reference to can also will be above 396eV, but to be less than N-O bond energys at 400eV；It is at 286.53eV
C-O keys, show that Ti-C keys are fragmented into for Ti-O-C keys.C, N doping hinders crystal growth, refines crystal, promotes ratio
The increase of surface area, more Lacking oxygens can be produced, the electric conductivity for being advantageous to nanometer rods improves.
Oxygen atom in N element substitution titanium dioxide lattice, forms Ti-N, and the energy gap between Ti-N lattices reduces,
The photocatalytic activity of titanium dioxide under visible light can be improved；Carbon atom is combined with oxygen atom, forms Ti-O-C-structure, is changed
Oxygen atom outermost electron, reduces TiO2Energy gap, electric conductivity enhancing.
Chlorohydric acid pickling is used before calcination, to maintaining calcination product heat endurance to have actively impact, promotes Anatase content
Increase, is advantageous to the raising of product photocatalytic activity；Reusability distilled water and alcohol flushing, to remove the ion on surface.
Gained codope Rutile Type TiO of the invention2Nanorod length is about 0.4 μm, width 10nm.
Brief description of the drawings
Fig. 1 is codope Rutile Type TiO of the present invention2Nanometer rods XPS schemes.
Fig. 2 is codope TiO2Photocatalysis Decomposition aquatic products hydrogen curve of the nanometer rods under ultraviolet lighting.
Fig. 3 is codope TiO2Photocatalysis Decomposition aquatic products hydrogen curve of the nanometer rods under ultraviolet-visible illumination.
Fig. 4 is codope Rutile Type TiO of the present invention2Nanometer rods TEM schemes.
Embodiment
Preparation method of the present invention is simple to operate, and course of reaction is gently stablized, easily controllable, realizes one-step synthesis C, N member
Plain codope Rutile Type TiO2Nanometer rods.With reference to specific embodiment, the present invention is further illustrated.
First, specific embodiment
Embodiment 1
0.06g titanium carbide is weighed, ultrasonic disperse adds 4mL ethylenediamine into 16mL distilled water, after disperseing 30min
Be fitted into 50mL hydrothermal reaction kettles, 180 DEG C of design temperature, the time be 6 hours, take out afterwards, naturally cool to 20 DEG C, pour into from
Centrifuged in heart pipe, using 2% watery hydrochloric acid pickling 2 times, afterwards using respectively washing 3 times of absolute ethyl alcohol and distilled water, done in constant temperature
Dried in dry case, temperature 70 C, time 12h, obtain product.Naturally cool to 20 DEG C and carry out subsequent operation, the control of temperature again
The synergy of C, N codope can be strengthened with the type of cooling, it is that titanium oxide pair can into the lattice of titanium oxide to make C, N doping
See the response enhancing of light, further improve catalytic degradation ability.
Embodiment 2
0.12g titanium carbide is weighed, ultrasonic disperse adds 5mL ethylenediamine into 17mL distilled water, after disperseing 30min
Be fitted into 50mL hydrothermal reaction kettles, 180 DEG C of design temperature, the time be 6 hours, take out afterwards, naturally cool to 20 DEG C, pour into from
Centrifuged in heart pipe, using 2% watery hydrochloric acid pickling 2 times, afterwards using respectively washing 3 times of absolute ethyl alcohol and distilled water, done in constant temperature
Dried in dry case, temperature 70 C, time 12h, obtain product.
Embodiment 3
0.18g titanium carbide is weighed, ultrasonic disperse adds 6mL ethylenediamine into 18mL distilled water, after disperseing 30min
Be fitted into 50mL hydrothermal reaction kettles, 180 DEG C of design temperature, the time be 6 hours, take out afterwards, naturally cool to 20 DEG C, pour into from
Centrifuged in heart pipe, using 2% watery hydrochloric acid pickling 2 times, afterwards using respectively washing 3 times of absolute ethyl alcohol and distilled water, done in constant temperature
Dried in dry case, temperature 70 C, time 12h, obtain product.
Embodiment 4
0.24g titanium carbide is weighed, ultrasonic disperse adds 7mL ethylenediamine into 19mL distilled water, after disperseing 30min
Be fitted into 50mL hydrothermal reaction kettles, 180 DEG C of design temperature, the time be 6 hours, take out afterwards, naturally cool to 20 DEG C, pour into from
Centrifuged in heart pipe, using 2% watery hydrochloric acid pickling 2 times, afterwards using respectively washing 3 times of absolute ethyl alcohol and distilled water, done in constant temperature
Dried in dry case, temperature 70 C, time 12h, obtain product.
Embodiment 5
0.30g titanium carbide is weighed, ultrasonic disperse adds 8mL ethylenediamine into 20mL distilled water, after disperseing 30min
Be fitted into 50mL hydrothermal reaction kettles, 180 DEG C of design temperature, the time be 6 hours, take out afterwards, naturally cool to 20 DEG C, pour into from
Centrifuged in heart pipe, using 2% watery hydrochloric acid pickling 2 times, afterwards using respectively washing 3 times of absolute ethyl alcohol and distilled water, done in constant temperature
Dried in dry case, temperature 70 C, time 12h, obtain product.
Embodiment 6
0.10g titanium carbide is weighed, ultrasonic disperse adds 4mL ethylenediamine into 16mL distilled water, after disperseing 20min
Be fitted into 50mL hydrothermal reaction kettles, 170 DEG C of design temperature, the time be 5 hours, take out afterwards, naturally cool to 20 DEG C, pour into from
Centrifuged in heart pipe, using 2% watery hydrochloric acid pickling 2 times, afterwards using respectively washing 3 times of absolute ethyl alcohol and distilled water, done in constant temperature
Dried in dry case, temperature 60 C, time 10h, obtain product.
Embodiment 7
0.15g titanium carbide is weighed, ultrasonic disperse adds 6mL ethylenediamine into 18mL distilled water, after disperseing 25min
It is fitted into 50mL hydrothermal reaction kettles, 160 DEG C of design temperature, the time is 5.5 hours, takes out afterwards, naturally cools to 20 DEG C, pour into
Centrifuged in centrifuge tube, using 2% watery hydrochloric acid pickling 2 times, afterwards using respectively washing 3 times of absolute ethyl alcohol and distilled water, in constant temperature
Dried in drying box, 65 DEG C of temperature, time 11h, obtain product.
Embodiment 8
0.27g titanium carbide is weighed, ultrasonic disperse adds 5mL ethylenediamine into 17mL distilled water, after disperseing 23min
It is fitted into 50mL hydrothermal reaction kettles, 175 DEG C of design temperature, the time is 5.7 hours, takes out afterwards, naturally cools to 20 DEG C, pour into
Centrifuged in centrifuge tube, using 2% watery hydrochloric acid pickling 2 times, afterwards using respectively washing 3 times of absolute ethyl alcohol and distilled water, in constant temperature
Dried in drying box, 75 DEG C of temperature, time 10.5h, obtain product.
Embodiment 9
0.25g titanium carbide is weighed, ultrasonic disperse adds 7mL ethylenediamine into 19mL distilled water, after disperseing 27min
It is fitted into 50mL hydrothermal reaction kettles, 165 DEG C of design temperature, the time is 5.3 hours, takes out afterwards, naturally cools to 20 DEG C, pour into
Centrifuged in centrifuge tube, using 2% watery hydrochloric acid pickling 2 times, afterwards using respectively washing 3 times of absolute ethyl alcohol and distilled water, in constant temperature
Dried in drying box, 80 DEG C of temperature, time 11.5h, obtain product.
Ultraviolet reflection spectral data are as follows：
Band gap magnitude is calculated by Kubelka-Munk equations：3.24eV(P25)、3.17(T1)、 3.04(T2)、
2.89eV (T3), 2.79eV (T4), 2.71eV (T5), so, there occurs the change that band gap narrows for C, N element doping.
Analyze to obtain from Fig. 1, several elements such as C, Ti, N, O are 285.1,530.4,399.8, the letter of 528.3eV positions
Number surface is present.
2nd, research and analysis
1st, the ratio control of titanium carbide and ethylenediamine of the present invention, obtained codope Rutile Type TiO2C, N in nanometer rods
Ratio, distribution are excellent, add the electric conductivity and wetability of nano composite material.Using the electrode of this material as working electrode,
Platinum plate electrode is that silver-colored silver chlorate is reference electrode, under 6mol/L KOH electrolyte, using CHI660E electrochemistry works to electrode
Make station and carry out electrochemical property test, such as Linear Circulation volt-ampere curve, constant current charge-discharge, AC impedance, there is high specific volume
Amount, good rate capability and cyclical stability.
2nd, Photocatalyzed Hydrogen Production activity research
The experiment is carried out in quartz reaction bottle, weighs 0.1g codope Rutile Type TiO of the present invention2Nanometer rods are put into
In 360mL quartz bottles, 200mL 0.1mol/L Na is added2S (98.0%, AR, Shanghai Ling Feng chemical reagent Co., Ltd) and
0.04mol/L Na2SO3The mixed solution of (97.0%, AR, Brassica rapa L analysis Chemical Industry Science Co., Ltd), experiment use light source
Respectively 8W uviol lamp (253.7nm, luminous intensity 0.75mW/cm2) and 500W xenon lamp (ultraviolet-visible light, Beijing are freely opened up
Science and Technology Ltd., luminous intensity 120mW/cm2).Before reaction, the first ultrasonic 15min of sample, then lead to N2Sealed after purging 30min
Closure system is placed in starting light-catalyzed reaction under light source, under magnetic stirring the h of continuous illumination 2, H caused by light-catalyzed reaction2Will
It is enclosed in the space in quartz reaction bottle on liquid level, gathers a gaseous sample from quartz reaction bottle per 20min and carry out H2
The quantitative analysis (GC7900 type gas chromatographs, Shanghai Techcomp Instrument Ltd.) of content, detector TCD, chromatogram
Post is 5A molecular sieves, N2Do carrier gas luminous intensities and pass through light power meter (ORIEL companies) and UV-A type ultraviolet radiation meter UV-A types
Ultraviolet radiation meter UV-254 (TaiWan, China Turner company) is measured.
Codope Rutile Type TiO of the present invention can be seen that by Fig. 2 and Fig. 32Catalysis production of the nanometer rods under uviol lamp
Hydrogen activity highest, 120min is up to 91.3 μm of ol, 45.65 μm of ol/h of hydrogen-producing speed；Hydrogen activity is produced in the catalysis of ultraviolet-visible light
It is 120min up to 12.4 μm of ol, 6.2 μm of ol/h of hydrogen-producing speed.
Comparative example product is carried out to the experiment of the same terms Photocatalyzed Hydrogen Production activity research, comparative example：Take Ti3C2 powders
50mg and 50mL aqueous solution of urea are stirred 2h, urea in aqueous solution of urea：The mass ratio of water is 1:1；By the solution of gained
It is put into water heating kettle, the hydro-thermal 12h at 160 DEG C, then by reacted powder deionized water and washes of absolute alcohol for several times,
Place into 40 DEG C of vacuum drying oven and dry, obtain C, N doping titanium dioxide nano rod.
From figures 2 and 3, it will be seen that comparative example codope TiO2Catalysis production hydrogen activity of the nanometer rods under uviol lamp
120min is up to 74.6 μm of ol, 37.3 μm of ol/h of hydrogen-producing speed；It is that 120min is reachable in the catalysis production hydrogen activity of ultraviolet-visible light
2.4 μm of ol, 1.2 μm of ol/h of hydrogen-producing speed.
Pass through Fig. 2 and Fig. 3, it can be seen that codope Rutile Type TiO of the present invention2Catalysis of the nanometer rods under uviol lamp
Hydrogen activity highest is produced, and it is also higher in the catalysis production hydrogen activity of ultraviolet-visible light, produce hydrogen activity in the catalysis of ultraviolet-visible light
Achieve breakthrough.
Claims (7)
- A kind of 1. codope Rutile Type TiO2The preparation method of nanometer rods, it is characterised in that using titanium carbide as raw material, by its point It is scattered in water, then adds ethylenediamine, disperse 20-30min, the feed liquid after disperseing is added in reactor, in temperature 160- At 180 DEG C, 5-6h is reacted, takes out, is cooled to 20 DEG C, through centrifuging, washing, dry, obtains codope Rutile Type TiO2Nanometer Rod.
- A kind of 2. codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, it is characterised in that carbon The mass volume ratio for changing titanium and ethylenediamine is (0.06g-0.30g)：(4mL-8mL).
- A kind of 3. codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, it is characterised in that point It is distilled water to be scattered in water water used, and the mass volume ratio of titanium carbide and distilled water is (0.06g-0.30g)：(16mL- 20mL)。
- A kind of 4. codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, it is characterised in that wash When washing, first with 2% watery hydrochloric acid pickling 2 times, then washed 3 times with absolute ethyl alcohol, finally with distillation washing 3 times.
- A kind of 5. codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, it is characterised in that dry When dry, it is dried using thermostatic drying chamber, drying temperature is 60-80 DEG C, drying time 10-12h.
- A kind of 6. codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, it is characterised in that point Dissipate and use ultrasonic disperse, it is 40-60Hz to control ultrasonic disperse frequency.
- A kind of 7. codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, it is characterised in that institute State reactor and use hydrothermal reaction kettle, the volume of reactor is 6-13 times of ethylenediamine volume used.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101074113A (en) * | 2007-05-16 | 2007-11-21 | 浙江大学 | Production and use for non-metallic doped nano-TiO |
| CN101332436A (en) * | 2008-08-06 | 2008-12-31 | 华中师范大学 | Low-temperature preparation method of titanium dioxide photocatalyst co-doped with carbon, nitrogen and sulphur |
| CN102527421A (en) * | 2011-11-10 | 2012-07-04 | 重庆工商大学 | C and N dual-doped nano TiO2 photochemical catalyst and preparation method thereof |
| CN106024416A (en) * | 2016-05-31 | 2016-10-12 | 陕西科技大学 | Nitrogen-doped rod-like titanium oxide/two-dimensional laminated titanium carbide nanometer composite electrode material, and preparation method and application therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101074113A (en) * | 2007-05-16 | 2007-11-21 | 浙江大学 | Production and use for non-metallic doped nano-TiO |
| CN101332436A (en) * | 2008-08-06 | 2008-12-31 | 华中师范大学 | Low-temperature preparation method of titanium dioxide photocatalyst co-doped with carbon, nitrogen and sulphur |
| CN102527421A (en) * | 2011-11-10 | 2012-07-04 | 重庆工商大学 | C and N dual-doped nano TiO2 photochemical catalyst and preparation method thereof |
| CN106024416A (en) * | 2016-05-31 | 2016-10-12 | 陕西科技大学 | Nitrogen-doped rod-like titanium oxide/two-dimensional laminated titanium carbide nanometer composite electrode material, and preparation method and application therefor |
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